摘要
聚烯烃类薄膜由于透明、易加工、价格低廉等优点而被广泛应用于食品、药品及电子元器件等商品的包装方面,但是,氧气、二氧化碳、水蒸气和有机小分子等物质易透过这些包装薄膜而影响被包装物的品质与寿命。
因此,为了提高常用的双向拉伸聚丙烯(BOPP)薄膜的阻隔性能以满足阻隔性包装的需要,本文采用溶胶-凝胶法,以正硅酸乙酯(TEOS)为前驱体、添加硅烷偶联剂γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)以提高涂层与基体的附着牢度、无水乙醇为共溶剂、盐酸为催化剂,在BOPP薄膜上负载SiO_2层。再以聚乙烯醇(PVA)和壳聚糖(CS)为有机物,制备PVA/SiO_2有机-无机杂化层和CS/SiO_2有机-无机杂化层。最终,制备了三种BOPP基阻隔性包装复合薄膜,并表征和测试其结构与性能。主要结论如下:
在SiO_2/BOPP阻隔性复合薄膜中,通过正交试验和单因素试验,分别讨论了KH560/TEOS摩尔比、无水乙醇量、去离子水量和盐酸量四个因素对复合薄膜阻隔性能的影响。确定制备SiO_2阻隔性复合薄膜原料的最佳摩尔配比为:(TEOS+KH560):乙醇:去离子水:盐酸=1:4:3:1.2,KH560:TEOS =2:3。此时,SiO_2复合薄膜的氧气阻隔性能是纯BOPP薄膜的21倍;水蒸气阻隔性能是纯BOPP薄膜的1.7倍;拉伸强度、断裂伸长率和透光率均优于纯BOPP薄膜。
在PVA/SiO_2/BOPP杂化阻隔性复合薄膜中,随PVA含量的增加,杂化复合薄膜的氧气阻隔性能提高,但水蒸气阻隔性能降低。当PVA质量分数为80%时,杂化复合薄膜的氧气阻隔性能是纯BOPP薄膜的308倍;但水蒸气阻隔性能是纯BOPP薄膜的一半;拉伸强度和断裂伸长率分别是纯BOPP薄膜的1.4倍和1.7倍;透光率大于90%,具有良好的透明性。
在CS/SiO_2/BOPP杂化阻隔性复合薄膜中,杂化层与BOPP薄膜紧密附着,表面无分相或开裂现象。随CS含量的增加,杂化复合薄膜的氧气阻隔性能先提高后降低;水蒸气阻隔性能持续降低。当CS质量分数为18%时,杂化复合薄膜的氧气阻隔性能是纯BOPP薄膜的112倍;水蒸气阻隔性能是BOPP薄膜的1.3倍;拉伸强度和断裂伸长率分别是纯BOPP薄膜的1.5倍和1.8倍;透光率低于纯BOPP薄膜,但仍具有良好的透明性。
Polyolefin films have been used widely in the food, pharmaceutical and electronic devices packaging industry because of their transparency, easy processability, low cost, and so on. However, these packaging films are permeable to oxygen, carbon dioxide, water vapor and volatile organic compounds, which affect the quality and lifetime of the products.
In order to improve the barrier property of the biaxially oriented polypropylene (BOPP) film and meet the barrier demands for packaging materials, SiO_2 coating, PVA/SiO_2 organic-inorganic hybrid coating and CS/SiO_2 organic-inorganic hybrid coating were prepared on BOPP film via sol-gel process, in our work. Tertaethoxysilane was used as the precursor. A silane-coupling agent ofγ-glycidoxypropyltrimethoxysilane (KH560) was used to improve the adhesion between the coated layer and the substrate film. In addition, absolute alcohol and hydrochloric acid were used as the co-solvent and the catalyst, respectively. Then, polyvinyl alcohol and chitosan were used as the organic compounds, respectively. As a result, three types of composite films compsosed of the coaing and the BOPP film were prepared. The structure and properties of these films were inspected. The main conclusions are as follows:
For the SiO_2/BOPP barrier composite films, the influences of KH560/TEOS molar ratio, absolute alcohol content , deionized water content and hydrochloric acid content were investigated on the barrier properties of the composite films by the use of orthogonal experiment and single factor experiments.As a result, the optimal technological parameters of preparation SiO_2 barrier composite films had been obtained. The molar ratio of (TEOS+KH560): absolute alcohol: deionized water: hydrochloric acid was optimized at 1:4:3:1.2, and the molar ratio of KH560 to TEOS was 2:3. At the same time, oxygen and water vapor barrier properties of SiO_2 composite films was 21 times and 1.7 times that of the bare BOPP film, respectively. Tensile strength, breaking elongation and the transmittance of SiO_2 composite films were better than BOPP film.
For the PVA/SiO_2/BOPP barrier hybrid composite films, with the increase of PVA content, the oxygen barrier property of the composite films was enhanced, while the water vapor barrier property of the composite films was dropped. As the mass ratio of PVA increased to 80%, the oxygen barrier property of the composite films was 308 times that of the pure BOPP film, however, water vapor barrier character was half of the BOPP film. At the same time, tensile strength and breaking elongation was 1.4 times and 1.7 times that of the pure BOPP film, respectively. The composite films had a good transparency due to the light transmission rate of was more than 90%.
For the CS/SiO_2/BOPP barrier hybrid composite films, the adhesion between hybrid layer and the BOPP substrate film was satisfactory. No phase separation and no creaking were observed on the surface of the coating. With the increase of CS content, the oxygen barrier property of the composite films was enhanced firstly and then decreased, while the water vapor barrier property of the composite films was dropped. As the mass ratio of CS increased to 18%, the oxygen and water vapor barrier characters of the composite films was 112 times and 1.3 times that of pure BOPP film, respectivly. At the same time, tensile strength and breaking elongation was 1.5 times and 1.8 times that of BOPP film, respectively. Although, light transmission rate was lower than that of the BOPP film, the composite films had a good transparency.
引文
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